Thio compounds as additives in fluids used in engines



3,546,117 THIO COMPOUNDS AS ADDITIVES IN FLUIDS USED IN ENGINES DonaldJ. Anderson, San Anselmo, Calif., assignor to Chevron Research Company,San Francisco, Calif., a corporation of Delaware No Drawing. Originalapplication June 3, 1965, Ser. No. 461,163, now Patent No. 3,449,440,dated June 10, 1969. Divided and this application Aug. 15, 1968, Ser.No. 761,387

Int. Cl. C10m 1/32, 1/38 US. Cl, 252-475 2 Claims ABSTRACT OF THEDISCLOSURE A lubricating oil composition is disclosed comprising an oilof lubricating viscosity and a detergency component of 25-250 carbonatoms, having the formula wherein the oxygen is bonded to the sulfur, Qis a C20-C245 aliphatic hydrocarbon radical, A is a C -C polyvalenthydrocarbon radical, Q is either a C -C hydrocarbon radical or asubstantially hydrocarbonaceous radical having 1-12 carbon atoms and anoxygen or nitrogen atom, n is 1 or 2, and m is 1, 2, or 3.

CROSS-REFERENCES TO RELATED APPLICATIONS This application is adivisional of application Ser. No. 461,163, filed on June 3, 1965 nowPat. 3,449,440 issued June 10, 1969.

This invention concerns novel sulfur derivatives which find use asdetergents in lubricating oils. More particularly, this inventionconcerns novel sulfur derivatives having one long chain hydrocarbonradical which find use as detergents in lubricating oils.

A development of major importance in the lubricating oil additive fieldhas been the introduction of ashless detergents, that is, metal freecompounds which are capable of reducing varnish and sludge deposits ininternalcombustion engines. An important advantage of these ashlessdetergents is the avoidance of the ash formed by the metal saltdetergents on decomposition. Thus, valve and combustion chamberdeposition with accompanying octane requirement increase can beminimized through their use.

A variety of lower molecular weight ashless detergents have beenreported in the patent literature. See for example U.S. Pat. No.3,018,251, which discloses acylated polyamines; US. Pat. No. 2,764,551,which discloses polyesters containing amino groups; US. Pat. No. 2,887,-452, which discloses urethanes; and US. Pat. No. 2,371,333, whichdiscloses esters of pentaerythritol, to mention a few.

It has'now been found that sulfur-containing compounds of from about 25to 250 carbon atoms having (1) From 1 to 3 sulfur-containingfunctionalities of the formula wherein n is a cardinal number of from to2, at the same end of the molecule; and

(2) An uninterrupted chain of at least 20 carbon atoms, preferably 25carbon atoms, can be used as ashless detergents in lubricating oils.Alternatively, the compounds of this invention have a long aliphatichydrocarbon chain as one part of the molecule and joined to this chainis a functionality having from 1 to 3 thioether groups bonded only tocarbon, i.e., -C-S'C; wherein United States Patent 0 ice from 0 to 2oxygens may be bonded to the sulfurs by coordinate covalent bonds.

Bonded to the short chain radical bonded to sulfur may be substituentswhich are inert (the substituents do not interfere with the preparationof the products or enhance or detract from the products utility) or doimpart desirable properties to the product. Illustrative of suchsubstituents are hydroxy, lower alkoxy, amino, lower alkyl amino anddi(lower alkyl) amino.

The molecule may be described by the following wherein Q is an aliphatichydrocarbon radical of from about 20 to 245 carbon atoms, A is apolyvalent (di-, trior tetra-substituted) hydrocarbon radical of from 1to 7 carbon atoms, usually an aliphatic hydrocarbon radical, Q is ahydrocarbon radical of from 1 to 8 carbon atoms, or a substitutedhydrocarbon radical of from 1 to 12 carbon atoms (see above), n is acardinal number of from 0 to 2 and 'm is an integer of from 1 to 3,usually of from 1 to 2.

The molecule may be further described, somewhat more narrowly, by thefollowing formula wherein R is an aliphatic hydrocarbon group, eithersaturated or having aliphatic unsaturation (e.g., olefinic unsaturation)of from about 2-0 to 245, usually 25 to about 150 carbon atoms, thesulfur substituent(s) being toward the end of the molecule (not morethan 6 carbon atoms from a terminal carbon atom), R is a hydrocarbylradical of from about 1 to 8 carbon atoms, more usually of from about 1to 3 carbon atoms or substituted hydrocarbyl radical of from 1 to 12carbon atoms and having from 0 to 1 atom of Row 2 of the Periodic Tableof atomic number 7 to 8, i.e., oxygen or nitrogen (hydrocarbyl is amonovalent organic radical composed solely of carbon and hydrogen whichmay be aliphatic, alicyclic, aromatic or combinations thereof, e.g.,alkaryl or aralkyl, and may have aliphatic unsaturation, e.g.,ethylenic), n is a cardinal number of from 0 to 2, m is an integer offrom 1 to 3, usually 1 to 2; when m is 2, the two R s may be joinedtogether to form a ring with the sulfurs to which the two R s areattached together with the intervening carbon atoms. When m is two orthree, the sulfur substituents will be separated by not more than fourcarbon atoms and usually not more than two carbon atoms.

Compounds wherein m is 1 have the following formula wherein R isaliphatic hydrocarbyl of from about 25 to 150 carbon atoms, preferablyof from about 30 to carbon atoms, R is hydrocarbyl of from 1 to 8 carbonatoms, preferably hydrocarbyl of from 1 to 3 carbon atoms andparticularly preferred alkyl of from 1 to 3 carbon atoms and n is acardinal number of from 0 to 2 or substituted hydrocarbyl as indicatedpreviously for R, preferably substituted alkyl of from 1 to 8 carbonatoms and 1 atom of atomic number 7 to 8.

When In is 2 or 3, the compounds have the following formula wherein R isaliphatic hydrocarbyl of from about 25 to carbon atoms, more usually offrom about 30 to 75 carbon atoms, R is hydrocarbyl of from 1 to 8 carbonatoms, more usually hydrocarbyl of from 1 to 3 carbon atoms andpreferably alkyl of from 1 to 3 carbon atoms and when the two R s aretaken together, hydrocarbylene of from 1 to 8 carbon atoms, preferablyalkylene of from 1 to 3 carbon atoms and n is a cardinal number of fromto 2 (hydrocarbylene is a divalent radical composed solely of carbon andhydrogen and otherwise the same as the definition of hydrocarbyl) and Ais a polyvalent (trior tetra-valent) aliphatic hydrocarbon radical whosevalences are satisfied by R and S[O] R and is of from 1 to 7 carbonatoms, usually of from 1 to 2 carbon atoms. R can also be substitutedhydrocarbyl as indicated for R As already indicated, two sulfur atomswill be separated by not more than four carbon atoms, and usually notmore than two carbon atoms; preferably, two sulfur atoms are separatedby from 1 to 2 carbon atoms.

As is evident from the above formulae, the compounds of this inventionare either mono-, dior tri-thioethers, sulfoxides or sulfones, wherein 1or more functionalities may be present. That is, the same molecule mayhave a sulfide and a sulfoxide or sulfone functionality. The followingformulae illustrate the various functionalities and indicate also thepreferred sub-genera.

a (II) R? R (I) IUSR O (I) R SCH; (II) R= CH 0 (IV) R CH 0 2 wherein R,R, R and R are as defined previously.

Illustrative of the various compounds of this invention are thefollowing: polyisobutenyl methyl sulfide, polyethylenyl methyl sulfide,polypropenyl methyl sulfide, poly-l-butenyl methyl sulfide,polyisobutenyl ethyl sulfide, polyisobutenyl hexyl sulfide, polypentenylcyclohexyl sulfide, polypropenyl tolyl sulfide, polyisobutenyl methylsulfoxide, polyisobutenyl phenyl sulfoxide, polypropenyl butylsulfoxide, polyisobutenyl methyl sulfone, polyisobutenyl ethyl sulfone,polyisobutenyl di(methylsulfenyl methane, polyethenyl di(ethylsulfonyl)methane, 2 polyisobutenyldithiolan 1,3,2 polypropenyldithiolan 1,3, 2polyisobutenyl 1,1,3,3 tetraoxodithiolan-1,3, 2 polyisobutenyl 1oxodithiolan 1 3, polyisobutenyl tris-(methylsulfonyl) methane,polypropenyl tri(ethylsulfonyl) methane, etc. (The polyalkenyl groupscan be either saturated or unsaturated having olefinic unsaturation andare from about to 150 carbon atoms.)

As already indicated, inert substituents may be present in the molecule.The substituents for the most part are hydroxyl, amino and lower alkylderivatives thereof. Illustrative of compositions having thesesubstituents are polypropenyl 2-hydroxyethyl sulfide, polyisobutenyl 2-ethoxyethyl sulfide, polyisobutenyl 3-isopropoxyethyl sulfoxide,polyisobutenyl 2 aminoethyl sulfone, polyiso- 1 (III) R" S CH;

4 butenyl N,N-diethylaminopropyl sulfide, polyethylenylN,N-dimethylaminoethyl sulfone, polyisobutenyl p-anisyl, sulfide,polypropenyl p-aminophenyl sulfone, etc.

Individual substituents are illustrated by amino, hydroxy,dimethylamino, pentylamino, ethoxy, propoxy, hexyloxy, etc.

The compounds of this invention can be prepared in a variety of waysaccording to known synthetic organic procedures. The sulfides can beprepared by combining the desired alkali metal sulfide with thepolyalkenyl halide, e.g., chloride or bromide. Preferably, the bromideis used since it appears to provide superior results in the engine.

The polyalkenyl halides can be obtained by polymerizing olefins fromabout 2 to 5 carbon atoms to a polymer of the desired molecular weight.Illustrative olefins are ethylene and propylene. Various methods knownin the art may be used, e.g., Lewis acid catalysts. The resultingpolymer will have residual unsaturation which can be used as the activesite for introduction of the halogen. Halogen may be introduced eitherionically or free radically.

The respective sulfoxides and sulfones can then be prepared by using avariety of oxidizing agents, hydrogen peroxide being the mostconvenient. The reaction is generally carried out in the presence of acarboxylic acid, which aids the oxidation of the sulfide to thesulfoxide or the sulfone.

The derivatives having more than one sulfur-containing functionality canbe prepared from disubstituted methanes, when the methylene group isactivated by a sulfonyl group, by preparing derivatives of a polyalkenylaldehyde, by forming the thiomercaptal, or other similar means.

The method of preparation is not critical to this invention and anyconvenient means known in the art for preparing the desired compoundsmay be used.

The following examples are offered by Way of illustration and not by wayof limitation.

EXAMPLE A Preparation of polyalkenyl halides (1) Into a reaction flaskwas introduced 1,350 g. of polyisobutene (1.5 moles, approximately 900molecular weight), the mixture cooled to about 20 C. and a solution of240 g. (1.5 moles) of bromine in 750 ml. of carbon tetrachloride addedover a period of 4 hours, while maintaining the temperature below 10 C.The mixture was then allowed to warm to room temperature with stirringand the solvent removed by heating to 100 C. at a pressure of 10 mm. Hg.The residue was then analyzed for bromine. Weight percent Br=9.46,indicating an equivalent weight of 846.

(2) Into a reaction flask was introduced 1,800 g. of polyisobutene (2moles, approximately 900 molecular weight) and 1.5 liters of benzene andthe solution cooled to 0 C. Over an 8-hour period, 142 g. of chlorine(20 moles) was bubbled into the benzene solution while maintaining thetemperature at about 0 C. An aliquot was taken and heated to 100 C. at 5mm. Hg. to remove any violatile material and the residue analyzed.Weight percent Cl=4.01, theory 3.9.

EXAMPLE 1 Preparation of polyisobutenyl methyl sulfide (A) Into areaction flask was introduced 162 g. (2.4 moles) of a weight percentaqueous potassium hydroxide solution and then diluted with 500 ml. ofabsolute ethanol. The solution was cooled with an ice bath, the flaskfitted with an acetone-Dry Ice condenser and then 106 g. (2.4 moles) ofmethyl mercaptan added to the solution. To the resulting potassiummethyl mercaptide was added 1,267 g. (1.2 moles, approximately 93 weightpercent of the bromide) of polyisobutenyl bromide (prepared as.describedin Example A-l) in 1 liter of benzene. The addition of the benzenesolution was at a rate which maintained the temperature below 36 C.After all of the benzene solution was added, the mixture was stirred andthen refluxed overnight.

The benzene phase was separated from the ethanolic phase, washed withwater until neutral and then dried over sodium sulfate. The benzene wasstripped in vacuo yielding 995 g.

Analysis.Weight percent S=2.55, theoretical=3.55, percent Br=0.727.

(B) Into a reaction flask was introduced 132 g. of 85 weight percentaqueous potassium hydroxide, 400 ml. of absolute ethanol, the solutioncooled in an ice bath and 96 g. (2 moles) of methyl mercaptan added. Theresulting potassium methyl mercaptide solution was then diluted with 400ml. of dioxane and 200 ml. of diethyl ether. A benzene solution (1,172g.) containing 80 weight percent polyisobutenylchloride (approximately900 molecular weight, 4.01 weight percent Cl) was diluted with 400 ml.of diethyl ether and the solution added to the above mixture. Thereaction mixture was then heated to reflux for one hour, the heatingstopped and the mixture allowed to stand overnight.

The reaction mixture was then repeatedly washed until neutral to pHpaper, dried over anhydrous sodium sulfate, filtered through celite andthe volatile material removed in vacuo. Yield: 841 g.

Analysis.-S=l.98% (theory, 3.7%), Molecular weight (ThermoNAM) 1022.

EXAMPLE 2 Preparation of a polyisobutenyl methyl sulfoxide (A) Into areaction flask was introduced 1,207 g. (0.925 mole) of polyisobutenylmethyl sulfide (prepared as described in Example 1-A) and 1 liter ofmethylene chloride, the mixture cooled at 20 C. and a solution of 104.8g. (0.925 mole) of 30 percent hydrogen peroxide added over a period of 1hour. At the end of this time, ml. of glacial acetic acid was added andthe mixture was heated to reflux (50 C.) and methylene chloridedistilled off. Benzene (100 ml.) was then added to assist the removal ofwater, a vacuum of l to 2 mm. Hg being applied when the pot temperaturereached 100 C. The residue weighed 1,200 g.

Analysis.--Weight percent S=2.01; molecular weight (ThermoNAM) 1,013.

v(B) Into a reaction flask was introduced 841 g. of the product ofExample 1-B, one liter of benzene, and 10ml. of glacial acetic acid. Tothis mixture was slowly added 59 ml. of 30 weight percent aqueoushydrogen peroxide. At the end of the addition, the mixture was heated to48 C. for a short time and then allowed to stand overnight.

After diluting the reaction mixture with one liter of ether, the etheralsolution was washed with water until neutral to pH paper, dried overanhydrous sodium sulfate and then stripped of volatile materials invacuo.

Analysis.-S=1.80%, Cl=1.40%, molecular weight (ThermoNAM):994.

EXAMPLE 3 Preparation of a polyisobutenyl sulfone Into a reaction flaskwas introduced 900 g. of sulfide prepared as described in Example 1(0.542 mole of sulfide, the remaining material being inert) 1.2 litersof benzene and 250 cc. of glacial acetic acid. To this mixture was added184.5 ml. of 30 weight percent aqueous hydrogen peroxide. At the end ofthe addition, the mixture was heated at reflux for 1 hour and allowed tostir overnight. To this mixture was then added 61.5 ml. of 30 weightpercent hydrogen peroxide and heated to reflux and held at thistemperature for 8 hours. An infrared spectrum of the product indicatedthe presence of sulfone. The reaction mixture was then washed with wateruntil neutral to pH paper, dried over anhydrous sodium sulfate, filteredthrough celite and the solvent stripped.

Analysis. Weight percent S=l.63 (theoretical: 1.89%

EXAMPLE 4 Preparation of polyisobutenyl bis (methylsulfonyl) methaneInto a reaction flask was introduced 950 ml. of absolute ethanol and 23g. of sodium dissolved in the ethanol. To the sodium ethoxide solutionwas then added 172 g. of bis-di-(methylsulfonyl) methane, after whichwas added 1,000 g. of polyisobutenyl bromide (prepared as described inExample A-l) dissolved in 1.5 liters of benzene and the reaction mixturemaintained at a temperature of about 50 C. The temperature was thenraised to reflux (71 C.) and maintained for 7.5 hours. At the end ofthis time, the reaction was allowed to cool, diluted with ether andWashed with water. After drying the solution, it was filtered and thevolatile material removed in vacuo.

Analysis.Weight percent 8:0.71 (theory=6.39).

EXAMPLE 5 Preparation of a polyisobutenyl sulfone having a hydroxylsubstituent (A) Into a reaction vessel was introduced g. (2.0 moles)sodium hydroxide and 250 ml. of absoluate ethanol, followed by thedropwise addition of Z-mercaptoethanol.

To the mercaptide prepared above was added 520 g. of polyisobutenylbromide (approximate molecular weight=550) in 500 ml. of benzene and themixture Was then heated at reflux for 18 hours. After allowing themixture to cool, the mixture was filtered and then extracted with 3aliquots of 250 ml. of Water. The solution was then neutralized by theaddition of 10 ml. conc. HCl and then washed with water until thewashings were neutral to pH paper. After drying over anhydrous sodiumsulfate, the volatile material was removed in vacuo. Yield=442 g.

Analysis.S=3.79, 3.75 percent, molecular weight (ThermoNAM)-=467.

(B) Into a reaction flask was introduced 442 g. (0.848 mole, approximatemolecular weight 520) of polyisobutenyl 2-hydroxyethyl sulfide, preparedas described above, 500 ml. of benzene and 20 ml. of glacial aceticacid. To this mixture was then added 287 g. (2.55 moles) of 30 percenthydrogen peroxide, the temperature rapidly rising to 60 C. After theaddition of the hydroperoxide was completed, the mixtre was stirred foran additional 3 hours and then heated at reflux for an additional 2hours. The infrared spectrum of an aliquot of the reaction mixture fromwhich the solvent had been removed indicated the presence of sulfone.The reaction mixture was then diluted with 500 ml. of ether, the organicphase separated from the aqueous phase, and then the organic phasewashed with water until neutral to pH paper. After drying the organicphase over anhydrous sodium sulphate, the volatile materials wereremoved in vacuo. The residue weighed 411 g.

Analysis.Weight percent S=2.95%, moleclar weight (ThermoNAM) =549.

EXAMPLE 6 Preparation of polyisobutenyl 2-aminoethyl sulfide (A) To 111g. (0.982 mole) of Z-aminoethanethiol hydrochloride was added 500 ml. ofabsolute ethanol and 50 ml. water, followed by the slow addition of129.4 g. (1.97 moles) of weight percent aqueous KOH while cooling thereaction mixture in an ice bath.

To the above mixture was then added 1,163 g. of polyisobutenyl bromide(82.7 weight percent active,

0.982 mole, approximately 900 molecular weight) and one liter of ether,the resulting mixture allowed to stand overnight, followed by heating atreflux throughout the following day. After allowing the mixture to cool,the mixture was washed with water until neutral to pH paper, dried overanhydrous sodium sulfate, filtered through celite and then the volatilematerials stripped in vacuo.

Analysis.-S=l.41, 1.42%; N=0.76, 0.75%; Br= 1.75%; moleclar weight(ThermoNAM)-= 1,139.

Preparation of polyisobutenyl Z-aminoethyl sulfoxide (B) To a mixture of911 g. (0.492 mole) of the sulfide prepared above, one liter of benzeneand 100 ml. of glacial acetic acid cooled in an ice bath, 55 ml. of 30Weight percent aqueous hydrogen peroxide was added over a one hourperiod. After stirring for an additional two hours, the reaction mixturewas diluted with pentane, washed with water, the acetic acid extractedwith dilute base, and then repeatedly washed, adding methanol tominimize the emulsion. After distilling the benzene-water azeotrope, theresidue was diluted with pentane, extracted with ethanol, and the twoprases stripped of volatiles.

Raflinate: Yield552 g.

Analysis.S=0.29% N=0.32, 0.30%.

Extract: Yield274 g.

Analysis.S=1.43%; N=0.73, 0.71%.

EXAMPLE 7 Alternative method of preparation polyisobutenyl methylsulfide Methyl disulfide (113 g., 1.2 moles) in 750 ml. of methylenechloride was cooled to 10 C. while maintaining a nitrogen atmosphere,followed by the addition of 85 g. (1.2 moles) of chlorine over a twohour period. The resulting mixture was added to 630 g. (2.0 moles) ofpolyisobutene (approximately 315 molecular weight) in 500 ml. methylenechloride at 20 C. After completion of the addition, volatile materialwas stripped in vacuo at 100 C., the residue treated with Norite, anactivated charcoal, for 1 hour at 100 C. and the charcoal removed byfiltration.

Yield=536 g.

Analysis.-S=3.53% (Theory=6.9); Cl=3.25%.

A number of other compounds were prepared according to methods describedin the previous examples. While some variations in the solvent ortemperature occurred, these were not found to significantly affect theproducts obtained or their subsequent performance in the engine. Thehigh molecular weight olefin used was polyisobutene,

either of 450 molecular weight or of about 900 molecular r weight. Boththe chloride and bromide were used, whichever one being indicated. Thesulfur analysis is reported both with the sulfide and, when applicable,the oxidized sulfur compound. The compounds are all polyisobutenylmethyl sulfides and their sulfoxide derivatives.

TABLE I Wt. percent sulfur Molecular weight Sulfide Sulfoxide(ThermoNAM) 2 1 Polyisobutene having approximate molecular weight: A=900; B=450.

1 Commercial differential diffusion method for molecular weightdctermination.

3 After preparing the sulioxide, the product was purged with nitrogensand then seated at 100 C. for 30 minutes at 10 mm. Hg. The analysis i,for the product after the thermal treatment.

As already indicated, the compounds of this invention find use asdispersants and detergents in lubricating oils. The compounds of thisinvention'find particular use in diesel engines, demonstrating excellentresults under the 8 high temperatures at which diesel engines operate.When compounded with a lubricating oil for use in an engine, thecompounds of this invention will be present in at least about 0.1 weightpercent and usually not more than 10 weight percent, more usually in therange of about 1 to weight percent.

The compounds, however, can be prepared as concentrates, due to theirexcellent compatibility with oils. As concentrates, the compounds ofthis invention will generally range from about to 70 weight percent,more usually from about to 50 weight percent of the total composition.

Usually included in the oils are other additives, such as extremepressure agents, rust inhibitors, antioxidants, oiliness agents, foaminhibitors, viscosity index improvers, pour point depressants andoccassionally other detergents. Usually, these will be present in therange from about 0.01 to 10 weight percent, more usually from about 0.5to 5 weight percent of the composition and generally each of theadditives will be present in the range from about 0.01 to 5 weightpercent of the composition.

A preferred aspect in using the compounds of this invention inlubricating oils is to include in the oil from about 10 to 50 mM./kg. ofa zinc 0,0-dihydrocarbyl phosphorodithioate, wherein the hydrocarbylgroups are from about 4 to carbon atoms, Usually, the hydrocarbyl groupswill be alkyl or alkaryl groups. Other phosphorodithioates may also beused with advantage.

The lubricating fluids which may be used with the compounds ofthisinvention (hereinafter referred to as oils) may be derived from naturalor synthetic sources. Oils generally have viscosities of from about to50,000 Saybolt Universal Seconds (SUS) at 100 F. Among naturalhydrocarbonaceous oils are paraffin base, naphthenic base, asphalticbase and mixed base oils. Illustrative of synthetic oils are:hydrocarbon oils, such as polymers of various olefins, generally of from2 to 6 carbon atoms, and alkylated aromatic hydrocarbons; andnonhydrocarbon oils, such as polyalkylene oxides, aromatic ethers,carboxylate esters, phosphate esters and silicon esters. The preferredmedia are the hydrocarbonaceous media, both natural and synthetic.

The above oils may be used individually or together, whenever miscibleor made so by the'use of mutual solvents.

In order to demonstrate the excellent effectiveness of the compounds ofthis invention as detergents and dispersants in lubricating oils, thecompounds were tested in the 1-G Caterpillar Test (MILL-45199conditions). The oil used was a Mid-Continent SAE 30 oil and 12 mM./kg.of zinc dialkylphenyl phosphorodithioate (the alkyl groups werepolypropylene of about 12 carbon atoms) was included.

TABLE II Wt. percent of Example detergent Groove Land Underhead No. inoil 1 deposits 1 deposits 3 deposits 4 fIhe weight percent is based onthe total non-volatile product obtamed, which generally contains about50 to of the sulfur-containing product. Therefore, all the values shouldbe reduced by from A to to indicate the weight percent of activematerial.

2 The groove deposits are rated on a scale of O to 0 is completelyclean, while 100 IS completely filled. Base oil containing the indicatedamount of phosphorodithioate is rated as 93-15-9-3.

3 The land deposits are rated on a basis of 0 to 800; 0 is completelyclean and 800 is completely black. Base oil containing the indicatedamount of pho i plhororitlhioaedis rated as 500-800-370.

e an or ea cposits are rated on a scale oi 0 to 10 0 is com letel black,while 10 is clean. I p y It is evident from the above table that thesulfides, sulfoxidcs and sulfones all provide excellent detergency underthe stringent conditions of the l-G Caterpillar Test. Of particular noteis the extremely clean underhead obtained in most of the examples.Moreover, it is possible that the presence of polyisobutenyl halide isdetrimental to maintaining clean pistons. By removing the undesirablehalides from the compounds of this invention, further improvement inoperating efiiciency in the engine could presumably be obtained.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, Without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

I claim:

1. A lubricating oil composition consisting essentially of an oil oflubricating viscosity selected from the group consisting of mineral oil,alkylated aromatic hydrocarbons and non-hydrocarbon lubricating oils andin a minor amount suflicient to provide detergency, a composition offrom 25 to 250 carbon atoms, of the formula wherein the oxygen is bondedsolely to the sulfur, Q is an aliphatic hydrocarbon radical of fromabout 20 to 245 carbon atoms, A is a polyvalent hydrocarbon radical offrom 1 to 7 carbon atoms, Q is a hydrocarbon radical of from 1 to 8carbon atoms or a substituted hydrocarbon radical having from 1 to 12carbon atoms wherein the substituent is selected from the groupconsisting of hydroxy, lower alkoxy, amino, lower alkylamino and di(low-10 er alkyl)amino, n is a cardinal number of from 1 to 2, and m is aninteger of from 1 to 3.

2. A lubricating oil composition comprising a major portion of an oil oflubricating viscosity and in a minor amount sufiicient to providedetergency, a composition of from 25 to 25 0 carbon atoms of theformula:

UNITED STATES PATENTS 3,390,086 6/1968 OHalloran 25247.5 2,257,969 10/1941 Loane et al. 252-48.2 2,318,629 5/1943 Prutton 252-48.2 2,947,7878/1960 Flanagan 252-48.2X 3,208,940 9/1965 Owens et a1. 25248.2X3,399,146 8/1968 Scanley 252l61X 3,382,180 5/1968 Priestley et al.2521-61X DANIEL E. WYMAN, Primary Examiner W. H. CANNON, AssistantExaminer US. Cl. X.R. 25248.2

@2 33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent 3.5%.117 Dated December 8 1970 Inventor-( J.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Col. 3, line 25, "(III) CR" should read -(III) RC-;

line 25, "(SR should read --(SR Col. 5, line 30, "3.7%" should read-3.37

Col. 6, line 30 "absoluate" should read -absolute--;

line 53 "mixtre should read -mixture--;

line 6 "moleclar" should read molecular.

Col. 7, line 9, "moleclar" should read --molecu1ar-;

line 70, "i," should read -is--.

Col. 8 third line of footnote 2 93-15-9-3" should read Col. 10 line 3,"comprising a major portion" should read --consisting essentially--;

lines 3-4, after "viscosity" and before "and" insert --selected from thegroup consistin of mineral oil, alkylated aromatic hydrocarbons andnon-hydrocarbon lubricating oils-. L. Signed and sealed this 8th day ofJune 1971 (SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, J'I

Attesting Officer Commissioner of Patent:

